CN106062533A - Breath measurement device, breath measurement method, and gas cell - Google Patents
Breath measurement device, breath measurement method, and gas cell Download PDFInfo
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- 238000005259 measurement Methods 0.000 title claims abstract description 50
- 238000000691 measurement method Methods 0.000 title 1
- 238000010521 absorption reaction Methods 0.000 claims abstract description 32
- 238000002835 absorbance Methods 0.000 claims description 45
- 230000005540 biological transmission Effects 0.000 claims description 18
- 230000003287 optical effect Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000012360 testing method Methods 0.000 claims description 8
- 230000008676 import Effects 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 4
- 238000009738 saturating Methods 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 39
- 239000007789 gas Substances 0.000 description 32
- 230000009102 absorption Effects 0.000 description 21
- 230000004888 barrier function Effects 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- 241000590002 Helicobacter pylori Species 0.000 description 6
- 229940037467 helicobacter pylori Drugs 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000003745 diagnosis Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000002496 gastric effect Effects 0.000 description 2
- 230000000155 isotopic effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 210000002784 stomach Anatomy 0.000 description 2
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 230000005428 wave function Effects 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
- G01N21/05—Flow-through cuvettes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/483—Physical analysis of biological material
- G01N33/497—Physical analysis of biological material of gaseous biological material, e.g. breath
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
- G01N2021/396—Type of laser source
- G01N2021/399—Diode laser
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
- G01N21/0332—Cuvette constructions with temperature control
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/06—Illumination; Optics
- G01N2201/061—Sources
- G01N2201/06113—Coherent sources; lasers
- G01N2201/0612—Laser diodes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/004—CO or CO2
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Abstract
This breath measurement device has a light source, a gas cell, and a detector. The light source emits ultraviolet light. The gas cell has an incident surface on which the infrared light impinges and an exit surface through which the infrared is transmitted, breath containing 13CO2 and 12CO2 being introduced into the gas cell. The length of the gas cell is 2.5-20 cm. The detector measures the first transmittance of transmitted light from the exit surface at a first wavelength within the wavelength band from among the absorption lines of the 13CO2, and the second transmittance of transmitted light from the exit surface at a second wavelength within the wavelength band from among the absorption lines of the 12CO2, and is capable of computing the respective concentrations of the 13CO2 and the 12CO2.
Description
Technical field
Embodiments of the present invention relate to expiratory measurements device and expiratory measurements method and air chamber (gas cell).
Background technology
The concentration of the various gases using infrared optical power measurement to exhale or to contain in environmental gas.
In the case of measuring expiration, by measuring such as CO2、CO、NH3、NO2、C2H2、CH4Deng gas concentration, with regard to energy
Enough know have without exception.
But, about the absorption spectrum of these gases, if gas concentration is high, then absorbing can be saturated, needs to be modified.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2013-515950 publication
Summary of the invention
Invent problem to be solved
A kind of expiratory measurements device reducing measurement error and expiratory measurements method and air chamber are provided.
Means for solving the above
The expiratory measurements device of embodiment has light source, air chamber and test section.Light source releases infrared light.Air chamber is for containing
Have13CO2With12CO2Expiration import, there is the plane of incidence incident for described infrared light and the outgoing for described infrared transmission
Face.A length of more than the 2.5cm in room of described air chamber and below 20cm.Test section measures the first absorbance and the second absorbance, it is possible to
Calculate described respectively13CO2With12CO2Concentration, described first absorbance is described13CO2Absorption Line in described wave band
The absorbance of the transmission light from described exit facet under first wave length, described second absorbance is described12CO2Absorption Line in
The transmission light from described exit facet under second wave length in described wave band.
Accompanying drawing explanation
Fig. 1 (a) is the pattern front view of expiratory measurements device of the present embodiment, and Fig. 1 (b) is that the pattern of air chamber is bowed
View.
Fig. 2 (a) is to represent that wave number is 2200～2400cm-1Time the chart of absorbance, Fig. 2 (b) be expressed as 2295～
2297cm-1Time the chart of absorbance.
Fig. 3 (a) is to represent that wave number is 2275～2325cm-1Time13CO2With12CO2The chart of absorptance, Fig. 3 (b)
It is expressed as 2295.7～2296.3cm-1Time the chart of absorptance.
Fig. 4 is the chart of the interdependence of the relative error representing gas concentration Relative Transmission degree.
Fig. 5 is the flow chart of the expiratory measurements method that embodiment relates to.
Fig. 6 (a) is the pattern axonometric chart of QCL, and Fig. 6 (b) is the pattern sectional view along A1-A2 line, and Fig. 6 (c) is to illustrate
The ideograph of the action of QCL.
Detailed description of the invention
Hereinafter, referring to the drawings, embodiments of the present invention are illustrated.
Fig. 1 (a) is the pattern front view of expiratory measurements device of the present embodiment, and Fig. 1 (b) is that the pattern of air chamber is bowed
View.
Expiratory measurements device has light source 10, air chamber 20 and test section 40.Light source 10 more than 4.34 μm and 4.39 μm with
Under wave band in release tunable wave length infrared light.Expiration BR or reference gas is imported in air chamber 20.Expiration BR contains13CO2With12CO2, in wave band, it is respectively provided with at least one Absorption Line.
Air chamber 20 has plane of incidence 20a and exit facet 20b for infrared light.The optical axis 10a of the incident illumination I0 of infrared light
The most orthogonal with plane of incidence 20a and exit facet 20b.The long L in room becomes along between the plane of incidence 20a and exit facet 20b of optical axis 10a
Distance, be such as set to more than 2.5cm and below 20cm.
Test section 40 is measured13CO2Absorption Line in the transmission light from exit facet 20b under first wave length in wave band
The first absorbance and12CO2Absorption Line in the transmission light from exit facet 20b under second wave length in wave band second
Absorbance, it is possible to calculate respectively13CO2With12CO2Concentration.
Light source 10 can be set to QCL (Quantum Cascade Laser: QCL), semiconductor laser
Deng.One of gas as object of expiratory measurements device has CO2.Can be according to the CO before and after picked-up reagent2The change of isotope ratio
Change and carry out stomach diagnosis.Infrared light from QCL or semiconductor laser is preferably laser, and this is due in the situation being laser
Under, easily become directional light, and by CO2Gas absorbs expeditiously.
The CO contained in the expiration of people2Concentration is about 0.5～8%.Additionally, CO2Infrared wavelength range have many from
The Absorption Line dissipated.Using the wavelength in wide infrared wavelength range in the present embodiment is that (be equivalent to wave number is 4.34 μm
2300cm-1More than) and 4.39 μm (being equivalent to wave number is 2280cm-1) following infrared light measures expiration (being venting one's pent-up feelings at this)
In about less than 8% gas concentration.
In order to make infrared light wavelength match with Absorption Line, use the light-emitting component 10b of tunable wave length.Such as, sending out
In the case of optical element 10b is QCL, emission wavelength is due to electric current or temperature and slight variation.Therefore, if making the driving electricity of QCL
Stream was changed relative to the time, just wavelength tuning can be become Absorption Line.Or, use peltier (Peltier) element etc. to make
The temperature of QCL is changed, and also can be tuned to Absorption Line.
Below, air chamber 20 is explained.The expiration output of people, is about 500 milliliters/time.If the capacity of air chamber 20
More than 500 milliliters, then can be affected by exhale (the dead space gas) do not replaced in lung, detection performance reduces.That is, air chamber 20
Capacity is preferably less than 500.Additionally, the shape of air chamber 20 can be such as diameter 16mm, the long L in room is the cylinder (volume of 20mm
It is about 4 milliliters) etc..
Air chamber 20 can have: has expiration BR or the introducing port 22 of reference gas (air etc.) of valve 23；And have
The outlet 24 of valve 25.If being connected in outlet 24 reduce pressure by vacuum pump (not shown), then the live width of Absorption Line just becomes
Carefully, tail off with the overlapping of adjacent Absorption Line.Therefore, it is possible to separate CO2Isotopic Absorption Line.The plane of incidence 20a of air chamber 20
Infrared light is had high-transmission rate window portion etc. can be set to exit facet 20b.
Expiratory measurements device can have thermostat layer 90 further, the inner containment air chamber 20 of this thermostat layer 90.Such as exist
The side of air chamber 20 arranges heater etc., and then about with heat-barrier material encirclement etc., thus thermostat layer 90 makes air chamber 20
Inside remains uniform temperature.Owing to the absorption coefficient of gas changes with gas temperature, therefore, by air chamber 20 is kept
For uniform temperature such that it is able to improve the certainty of measurement of gas concentration.It addition, as shown in this figure, by from introducing port 22 to quilt
The roundabout configuration in measurement portion 28 small-bore conduit 26a, 26b, 26c, 26d, 26e, thus enable that when injecting measured portion 28
Gas temperature becomes the temperature in air chamber 20 near temperature.
In the case of importing the reference gas such as air in the air chamber 20 of expiratory measurements device, will be in transmission under first wave length
The intensity of the light of the reference gas imported in air chamber 20 is equal to incident intensity, it is possible to calculate the first absorbance.
Additionally, the light intensity of reference gas is equal to incident intensity by transmission under second wave length, it is possible to calculate second saturating
Penetrate rate.The most repeatedly carry out the measuring process of object gas and the measuring process of reference gas.Can will measure letter further
Number value equalization, improve measurement of concetration precision.
Test section 40 can include light accepting part 40a or data processing division 40b.Light accepting part 40a can be photodiode or
Cooling type detector (being made up of MCT:HgCdTe) etc..
Expiratory measurements device can have further: incident section 50, arranges near plane of incidence 20a, makes from light-emitting component 10b
The infrared light dissipated becomes directional light；With exit portion 60, arrange near exit facet 20b, directional light is focused on towards test section.Logical
Cross and make air chamber 20 side of lens 50a become plane, and make air chamber 20 side of lens 60a become plane, it is possible to make
Become certain by the optical length of the directional light of object gas, thus improve certainty of measurement further.So, it is possible to make to lead to
The optical length crossing air becomes such as below 7mm, it is possible to reduce the impact etc. disturbing gas in air.
Fig. 2 (a) is to represent that wave number is 2200～2400cm-1Time the chart of absorbance, Fig. 2 (b) be expressed as 2295～
2297cm-1Time the chart of absorbance.
The longitudinal axis is absorbance, and transverse axis is wave number (cm-1).Additionally, measuring condition is CO2Concentration: 4%, pressure: 1 atmospheric pressure,
Temperature 296K.
First, formula (1) represents langbobier law.This law precision for low density gas is higher, if but gas concentration
Uprise, then absorb saturated, it is therefore desirable to revise.Further, absorption coefficient is determined by the intensity of Absorption Line, pressure, temperature.
[mathematical expression 1]
Wherein, A: absorbance
I0: incident intensity
I: transmitted intensity
T: absorbance
α: absorptance
L: optical length
Further, in Fig. 2 (a), Fig. 2 (b), following formula represent absorbance.
Absorbance=1-I/I0=1-T
As shown in Fig. 2 (a), absorbance extends in a wide range,13CO2With12CO2Overlap and spectral shape are different.Such as,
When using infrared lamp (can also be with filter combination) as light source, need to measure many absorptions of the spectrum after constituting extension
Line also carries out data process.Additionally, be 2300～2360cm in wave number-1In the case of absorbance close to 1, close to absorption
Saturated.Therefore, become big from the deviation of langbobier law, create the necessity using calibration curve table etc. to be modified.Its knot
Really, data processing complex, measurement error becomes big.
Fig. 3 (a) is to represent that wave number is 2275～2325cm-1Time13CO2With12CO2The chart of absorptance, Fig. 3 (b)
It is expressed as 2295.7～2296.3cm-1Time the chart of absorptance.
Set CO again2Concentration is 8%, and pressure is 0.5 atmospheric pressure, and temperature is 313K.
The CO contained in the expiration of people2Concentration is 0.5～8% etc..To this, in the present embodiment, wave-length coverage is contracted
Narrow is 2280～2300cm-1, keep absorbance less than 1 so that in natural isotope ratio13CO2With12CO2Absorbance become
Same degree.Accordingly, it is capable to reduction measurement error.Additionally, Fig. 3 (b) represents ripple when isotopic Absorption Line contains 1 respectively
Number scope.Absorption coefficient is 0.55cm-1Below.
Below, the method using isotope detection helicobacter pylori is illustrated.Such as, people drinks into containing13C-urinates
The reagent of element is as labelled compound.If gastric has helicobacter pylori, reagent and helicobacter pylori reaction to discharge13CO2
Gas is as feeling elated and exultant.On the other hand, if there is no helicobacter pylori, would not discharge13CO2.Therefore, by measuring13CO2With12CO2Isotope ratio, it is known that infect helicobacter pylori degree, stomach diagnosis can be carried out accurately.Further, inspection
Check as being not limited to helicobacter pylori.By measuring containing isotopic CO2Concentration, it is possible to Diagnosis of Gastric on a large scale
Discharge ability.
Fig. 4 is the chart of the interdependence of the relative error representing gas concentration Relative Transmission degree.
First, absorption coefficient can use formula (2) to represent.
[mathematical expression 2]
α=ε c formula (2)
Wherein, ε: molar absorption coefficient
If the formula of use (1) and formula (2), then molar concentration c formula (3) represents.
[mathematical expression 3]
Wherein, c: molar concentration
The rate of change of molar concentration c relative transmittance T can use formula (4) to represent.
[mathematical expression 4]
Dc/c formula (5) represents.Relative error can be defined as the absolute value (ABS) of dc/c, by function (T × InT)-1
Determine.
[mathematical expression 5]
As shown in Figure 4, there is minima in relative error.Becoming minimum is at d (T × InT)-1During/dT=0, its condition is used
Formula (6) represents.
[mathematical expression 6]
LnT+1=0 formula (6)
According to formula (6), relative error becomes minimum absorbance T formula (7) and represents.
[mathematical expression 7]
Wherein, Top: relative error becomes minimum absorbance
E: index
That is, during Top=1/e, absorbance A=-1nT=1.
Fig. 5 is the flow chart of the expiratory measurements method that embodiment relates to.
Expiratory measurements method comprises the steps: to import in the air chamber 20 that the long L in room is more than 2.5cm and below 20cm to contain
Have13CO2With12CO2Expiration (S100)；In the way of making absorbance T become more than 0.07 and less than 0.75, shine towards expiration BR
First wave length is have selected in penetrating the wave-length coverage more than 4.34 μm and below 4.39 μm13CO2Absorption Line and second wave length
's12CO2The infrared incident illumination GI (S102) of wavelength of Absorption Line；Measure the of under first wave length transmission air chamber 20
One absorbance and under second wave length transmission second absorbance (S104) of air chamber 20；Calculate13CO2With12CO2Concentration
(S106)。
Further, expiratory measurements method can have following step further: import reference gas in air chamber 20, if first
Under wavelength, the light intensity of transmission reference gas is equal to incident intensity, calculates the first absorbance, if transmission under second wave length
The light intensity of reference gas, equal to incident intensity, calculates the second absorbance.
The CO of the expiration of people2There is individual variation in concentration, about 0.5～8%.Additionally, its median is about 4%.
According to the measurement of inventor, at CO2When concentration is 4%, wave number is 2380～2300cm-1Time absorption coefficient be 0.05～
0.4cm-1(wherein, pressure is 0.5 atmospheric pressure, and temperature is 313K).At this moment, preferably air chamber long Lop formula (8) represents.
Lop=-InTop/ α=1/ α formula (8)
(table 1) represents the long Lop of preferred air chamber of relative absorption coefficient α.
[table 1]
| α(cm-1) | Lop(cm) |
| 0.05 | 20.0 |
| 0.1 | 10.0 |
| 0.2 | 5.0 |
| 0.3 | 3.3 |
| 0.4 | 2.5 |
That is, if making absorption coefficient is 0.05～0.4cm-1As long as, then preferably air chamber long Lop more than 2.5cm and 20cm with
Lower.
In the case of the measurement error of absorbance T is certain, absorbance T is 1 ± 0.5%, and the width of absorbance A is 4.2
～5.3, error is greatly to 23.85%.Additionally, in the case of absorbance T is 99 ± 5%, the width of absorbance A be 0.005～
0.015, error reaches more than 100%.On the other hand, use the long L in room be selected as 2.5cm～20cm air chamber 20 (4.34～
4.39 μm) absorbance T that measures between 0.07～0.75 time, measurement error is reduced to less than 5%.Therefore, it is possible to very
Highland keeps the certainty of measurement of gas concentration c.
Below, the QCL used light source illustrates.
Fig. 6 (a)～Fig. 6 (c) is the ideograph of QCL.
Fig. 6 (a) is the pattern axonometric chart of QCL, and Fig. 6 (b) is the pattern sectional view of the A1-A2 line along Fig. 6 (a), Fig. 6
C () is the ideograph of the action illustrating QCL.
In this example embodiment, use the semiconductor light-emitting elements 30aL of QCL as light source portion 10.
As shown in Fig. 6 (a), semiconductor light-emitting elements 30aL includes substrate 35, laminate the 31, first electrode 34a, the second electricity
Pole 34b, dielectric layer 32 (first medium layer) and insulating barrier 33 (second dielectric layer).
It is provided with substrate 35 between the first electrode 34a and the second electrode 34b.Substrate 35 include Part I 35a, second
Part 35b and Part III 35c.These are partly arranged in a face.This face with from the first electrode 34a towards the second electrode
The direction of 34b intersects (the most parallel).Part III 35c it is configured with between Part I 35a and Part II 35b.
It is provided with laminate 31 between Part III 35c and the first electrode 34a.At Part I 35a and the first electrode
It is provided with dielectric layer 32 between 34a and between Part II 35b and the first electrode 34a.At dielectric layer 32 and the first electrode
Insulating barrier 33 it is provided with between 34a.
Laminate 31 has shape of stripes.Laminate 31 plays a role as ridge waveguide RG.2 ends of ridge waveguide RG
Face becomes minute surface.The light 31L released in laminate 31 penetrates from end face (light emergence face).Light 31L is infrared laser.Light
The optical axis 31Lx of 31L is along the extending direction of ridge waveguide RG.
As shown in Fig. 6 (b), laminate 31 such as include the first clad 31a, the first guide layer 31b, active layer 31c,
Two guide layer 31d, the second clad 31e.These layers are along pressing said sequence row towards the direction of the first electrode 34a from substrate 35
Row.The refractive index of the first clad 31a and the refractive index of the second clad 31e be respectively lower than the first guide layer 31b refractive index,
The refractive index of active layer 31c and each refractive index of the refractive index of the second guide layer 31d.The light produced in active layer 31c
31L is limited in laminate 31.Sometimes the first guide layer 31b and the first clad 31a is collectively referred to as clad.Sometimes by
Two guide layer 31d and the second clad 31e are collectively referred to as clad.
Laminate 31 has the first side 31sa and the second side 31sb being perpendicular to optical axis 31Lx.First side 31sa with
Distance 31w (width) between second side 31sb is below more than such as 5 μm and 20 μm.So, such as horizontal cross pattern
Control become easy, the raising of output becomes easy.If distance 31w is long, then under horizontal cross pattern, easily produce height
Order mode, it is difficult to improve output.
The refractive index of dielectric layer 32 refractive index less than active layer 31c.So, dielectric layer 32 is utilized and along optical axis 31Lx
Form ridge waveguide RG.
As shown in Fig. 6 (c), active layer 31c such as has cascade structure, in cascade structure, and the most alternately stacking
One region r1 and second area r2.Unit structure r3 includes first area r1 and second area r2.It is provided with multiple unit structure
r3。
Such as, in the r1 of first area, it is provided with the first barrier layer BL1 and the first quantum well layer WL1.At second area r2
In be provided with the second barrier layer BL2.Such as, in other first area r1a, it is provided with the 3rd barrier layer BL3 and the second quantum
Well layer WL2.It is provided with the 4th barrier layer BL4 in other second area r2a.
The intersubband optical transition of the first quantum well layer WL1 is produced in the r1 of first area.Thus release such as wavelength 3
Light 31La more than μm and below 18 μm.
Can the energy of carrier c1 (such as, electronics) that injects from first area r1 of relaxation in second area r2.
In quantum well layer (such as, the first quantum well layer WL1), trap width WLt is such as below 5nm.At trap width WLt
Such narrow time, energy level disperse, such as produce the first subband WLa (high level Lu) and the second subband WLb (low-lying level Ll) etc..From
The carrier c1 that one barrier layer BL1 injects is effectively limited in the first quantum well layer WL1.
When carrier c1 transits to low-lying level Ll from high level Lu, release and energy difference (high level Lu and low-lying level Ll
Difference) corresponding light 31La.That is, optical transition is produced.
Similarly, the second quantum well layer WL2 of other first area r1a releases light 31Lb.
In embodiments, quantum well layer can also comprise multiple traps that wave function overlaps.Multiple quantum well layers are each
High level Lu can also be the most identical.Respective low-lying level Ll of multiple quantum well layers can also be the most identical.
Such as, in certain of conduction band and valence band, intersubband optical transition is produced.Such as, hole based on pn-junction
With the compound of electronics it is not necessary to.Such as, a certain carrier c1 of hole and electronics produce optical transition, and put
Go out light.
In active layer 31c, such as, utilize the voltage being applied between the first electrode 34a and the second electrode 34b, via gesture
Barrier layer (such as, the first barrier layer BL1), injects carrier c1 (such as, electricity to quantum well layer (such as, the first quantum well layer WL1)
Son).Thus produce intersubband optical transition.
Second area r2 such as has multiple subband.Subband e.g. micro-strip.Energy difference in subband is less.Subband is preferred
Close with carrying continuously.Its result, the energy of carrier c1 (electronics) is relaxed.
In second area r2, the most do not release such as light (such as, infrared more than wavelength 3 μm and below 18 μm
Line).The carrier c1 (electronics) of low-lying level Ll of first area r1 is injected into second area r2 by the second barrier layer BL2, and
Relaxed.Carrier c1 is injected into the other first area r1a that cascade connects.Optics is produced in the r1a of this first area
Transition.
In cascade structure, each unit structure r3 of multiple unit structure r3 produces optical transition.So, easily
Higher light output is obtained in whole active layer 31c.
In this wise, light source 10 includes semiconductor light-emitting elements 30aL.Semiconductor light-emitting elements 30aL utilizes multiple SQW
The energy relaxation of the electronics in the subband of (such as, the first quantum well layer WL1 and the second quantum well layer WL2 etc.), actinometry light
30L。
Quantum well layer (such as, the first quantum well layer WL1 and the second quantum well layer WL2 etc.) uses such as InGaAs.Such as,
Barrier layer (such as, first～the 4th barrier layer BL1～BL4 etc.) such as uses InAlAs.At this moment, if using such as InP conduct
Substrate 35, then obtain good Lattice Matching in quantum well layer and barrier layer.
First clad 31a and the second clad 31e such as contains Si as p-type impurity.Impurity concentration in these layers
For such as 1 × 1018cm-3Above and 1 × 1020cm-3Below (such as, about 6 × 1018cm-3).These layer of respective thickness is
Such as more than 0.5 μm and below 2 μm (such as, about 1 μm).
First guide layer 31b and the second guide layer 31d such as contains Si as p-type impurity.Impurity concentration in these layers
For such as 1 × 1016cm-3Above and 1 × 1017cm-3Below (such as, about 4 × 1016cm-3).These layer of respective thickness is
Such as more than 2 μm and (such as, 3.5 μm) below 5 μm.
Distance 31w (width of laminate 31, the i.e. width of active layer 31c) is below more than such as 5 μm and 20 μm (example
As, about 14 μm).
A length of such as more than the 1mm of ridge waveguide RG and below 5mm (such as, about 3mm).Semiconductor light-emitting elements
30aL such as carries out action under the operation voltage of below 10V.Compared with consuming electric current and carbon dioxide laser device etc. relatively low.
So can carry out the action of low consumpting power.
Expiratory measurements device according to present embodiment and expiratory measurements method, using the teaching of the invention it is possible to provide one reduces measurement error
Expiratory measurements device and expiratory measurements method.
Have been described that several embodiments of the invention, but these embodiments propose as an example, and
It is not intended to limit invention scope.These new embodiments can be implemented in other various modes, can without departing from
Carry out various omission in the range of inventive concept, replace, change.These embodiments or its deformation are included in invention model
Enclose or in purport, and be also contained in invention and the equivalency range thereof of claims record.
Claims (14)
1. an expiratory measurements device, wherein, including:
Light source, releases infrared light；
Air chamber, for containing13CO2With12CO2Expiration import, there is the plane of incidence incident for described infrared light and for described infrared
Light transmissive exit facet, the room with more than 2.5cm and below 20cm is long；And
Test section, measures the first absorbance and the second absorbance, it is possible to calculate described respectively13CO2With described12CO2Concentration, institute
It is described for stating the first absorbance13CO2Absorption Line in saturating from described exit facet under first wave length in described wave band
Penetrating the absorbance of light, described second absorbance is described12CO2Absorption Line under second wave length in described wave band from
The absorbance of the transmission light of described exit facet.
Expiratory measurements device the most according to claim 1, wherein, farther includes:
Incident section, the near-earth that connects with the described plane of incidence arranges, makes described infrared light become directional light；And
Exit portion, the near-earth that connects with described exit facet arranges, makes described parallel light focusing.
Expiratory measurements device the most according to claim 2, wherein,
The optical axis of described infrared light is the most orthogonal with the described plane of incidence and described exit facet.
Expiratory measurements device the most according to claim 1, wherein, described infrared light is more than 4.34 μm and below 4.39 μm
Wave band in wavelength can tune.
Expiratory measurements device the most according to claim 4, wherein, releases described infrared light from QCL.
Expiratory measurements device the most according to claim 1, wherein, described test section sets under described first wave length transmission institute
The intensity of the light after the reference gas imported in stating air chamber, equal to incident intensity, calculates described first absorbance, if
Under described second wave length, the intensity of light after the described reference gas of transmission is equal to incident intensity, calculates described second saturating
Penetrate rate, and calculate described concentration.
Expiratory measurements device the most according to claim 6, wherein, farther includes:
Incident section, the near-earth that connects with the described plane of incidence arranges, makes described infrared light become directional light；And
Exit portion, the near-earth that connects with described exit facet arranges, makes described parallel light focusing.
Expiratory measurements device the most according to claim 1, wherein, the capacity of described air chamber is less than 500 milliliters.
Expiratory measurements device the most according to claim 1, wherein, is set to reduce pressure by the inside of described air chamber.
Expiratory measurements device the most according to claim 1, wherein, farther includes thermostat layer, in described thermostat layer
Portion accommodates described air chamber.
11. 1 kinds of expiratory measurements methods, wherein,
To room, the air chamber of a length of more than 2.5cm and below 20cm imports containing described13CO2With described12CO2Expiration,
Infrared incident illumination is irradiated towards described expiration,
Measure under described first wave length air chamber described in transmission the first absorbance and under described second wave length gas described in transmission
Second absorbance of room,
Calculate described13CO2With described12CO2Concentration.
12. expiratory measurements methods according to claim 11, wherein, described expiration is directed to post-decompression described air chamber
In.
13. expiratory measurements methods according to claim 11, wherein, about described infrared incident illumination, so that absorbance becomes
It is the mode of more than 0.07 and less than 0.75, in the wave-length coverage more than 4.34 μm and below 4.39 μm, selects described first wave
Long is described13CO2Absorption Line and described second wave length described12CO2The wavelength of Absorption Line.
14. 1 kinds of air chambers, wherein, including:
The plane of incidence of infrared light；
The exit facet of described infrared light；
Have the first valve, exhale and the introducing port of reference gas；And
There is the second valve, described expiration and the outlet of described reference gas,
A length of more than the 2.5cm in room of described air chamber and below 20cm, make described first valve and described second valve become closedown shape
Capacity during state is less than 500 milliliters.
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| JP2015-008899 | 2015-01-20 | ||
| JP2015008899 | 2015-01-20 | ||
| PCT/JP2015/076992 WO2016117173A1 (en) | 2015-01-20 | 2015-09-24 | Breath measurement device, breath measurement method, and gas cell |
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| CN106062533A true CN106062533A (en) | 2016-10-26 |
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| Country | Link |
|---|---|
| US (1) | US20160377533A1 (en) |
| JP (1) | JPWO2016117173A1 (en) |
| CN (1) | CN106062533A (en) |
| WO (1) | WO2016117173A1 (en) |
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| CN110402384A (en) * | 2017-01-20 | 2019-11-01 | 积水医疗株式会社 | Carbon isotope analysis device and carbon isotope analysis method |
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| US10571334B2 (en) | 2017-12-15 | 2020-02-25 | Horiba Instruments Incorporated | System and method for selective resolution for concave grating spectrometer |
| CN112703391A (en) * | 2018-09-28 | 2021-04-23 | 株式会社富士金 | Concentration measuring method |
| CN114270169A (en) | 2019-09-18 | 2022-04-01 | 株式会社富士金 | Concentration measuring device |
| US12078590B2 (en) * | 2020-03-13 | 2024-09-03 | Tokushima University | Concentration measuring method, and concentration measuring device |
| US11573174B2 (en) * | 2021-01-25 | 2023-02-07 | Advanced Energy Industries, Inc. | Optical gas concentration measurement apparatus |
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| Publication number | Publication date |
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| WO2016117173A1 (en) | 2016-07-28 |
| US20160377533A1 (en) | 2016-12-29 |
| JPWO2016117173A1 (en) | 2017-04-27 |
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